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WO1997011110A1 - Procede pour diminuer la couleur d'une emulsion contenant une cire polyolefinique modifiee chimiquement - Google Patents

Procede pour diminuer la couleur d'une emulsion contenant une cire polyolefinique modifiee chimiquement Download PDF

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Publication number
WO1997011110A1
WO1997011110A1 PCT/US1996/015013 US9615013W WO9711110A1 WO 1997011110 A1 WO1997011110 A1 WO 1997011110A1 US 9615013 W US9615013 W US 9615013W WO 9711110 A1 WO9711110 A1 WO 9711110A1
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WIPO (PCT)
Prior art keywords
emulsion
wax
color
hydrogen peroxide
weight percent
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Application number
PCT/US1996/015013
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English (en)
Inventor
Paul Andrew Rundquist
Ernest Phillip Smith
Stephen Louis Poteat
Dante Joseph Rutstrom
Richard Kingsley Stuart, Jr.
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Eastman Chemical Company
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Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to AU70758/96A priority Critical patent/AU7075896A/en
Publication of WO1997011110A1 publication Critical patent/WO1997011110A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2391/06—Waxes

Definitions

  • Wax emulsions are referred to as nonionic, anionic, or cationic, depending on the nature of the surfactant used to prepare the emulsion.
  • Fine particle wax emulsions, especially emulsions of functionalized synthetic polyolefin waxes are common additives in floor polish formulations.
  • Functionalized polyolefin waxes which are easily emulsified into the particles having fine size and narrow size distribution are prepared by f unctionalizing the wax according to methods such as oxidation and maleation to make the wax more hydrophilic.
  • "Functionalized polyolefin waxes" as used herein refers to either a homopolymeric or heteropolymeric polyolefin molecule which has been altered by the free radical or other type of addition or grafting of a hydrophilic side chain onto the hydrophobic polyolefin backbone, wherein the side chain group could be derived from a single molecule or an oligomer of an acid or anhydride functional species such as acrylic acid or maleic anhydride, and the like.
  • Heteropolymeric polyolefin molecules are copolymers which typically contain one alpha-olefin copolymerized with another polyolefin, usually a minor amount, such as a copolymer of ethylene containing up to 10 weight percent of another alpha-olefin.
  • Functionalized waxes prepared either through air oxidation with or without a catalyst, or by reaction with acid or anhydride functional species such as acrylic acid or maleic anhydride, are easily emulsified as fine sized particles in water with the aid of surfactants. Air oxidation results in the formation of polar carboxylic acid groups covalently bound to the wax. Examples of air oxidized polyolefins and air oxidation processes are disclosed in U.S.
  • Patents 2,879,239; 3,519,588 and 3,329,667 Reaction with maleic anhydride, commonly called “maleation,” results in the formation of hydrophilic dicarboxylic acid/anhydride groups covalently bound to the wax.
  • maleated polyolefins are disclosed in U.S. Patents 3,480,580 and 3,642,722.
  • the functionality of the synthetic waxes used to prepare wax emulsions is crucial for determining end-product application performance of the emulsion.
  • Emulsions having the application performance properties required for use as floor polish additives or similar coating applications contain functionalized polyolefin wax typically having a molecular weight greater than 1 ,000.
  • Floor polish products having a substantially colorless or water-white color are generally preferred by consumers. Even a lightly colored emulsion that merely appears dirty or dingy is considered to be colored since it is aesthetically unpleasant.
  • emulsion color is a critical criterion for marketability of a wax emulsion as a floor polish additive. Strictly controlled emulsification conditions and the addition of sodium metabisulfite, a reducing agent, are known to somewhat minimize the color of wax emulsions. However, even with strictly controlled conditions, the functionalized polyolefin wax emulsion is still colored, too highly colored for general consumer acceptance.
  • the present invention is a method of treating a colored emulsion of functionalized polyolefin wax with a water soluble oxidizing agent at a temperature which is above the freezing point of the emulsion and below both the boiling point of the emulsion and the softening point of the wax for a time sufficient to affect a significant reduction in emulsion color.
  • Another aspect of this invention is the novel essentially colorless emulsion of functionalized polyolefin wax, produced according to this new method, which exhibits essentially the same application performance properties as it would have prior to the color reduction process.
  • the applicants have unexpectedly discovered a process for significantly reducing the color of an emulsion of functionalized polyolefin wax.
  • the treatment of an emulsion of functionalized polyolefin wax according to this process not only reduces color but does so while maintaining the application performance properties of the wax emulsion.
  • the novel process of the present invention can be used to significantly decolorize an emulsion of functionalized polyolefin wax.
  • the applicants have found that there is a strong correlation between the color of the functionalized wax prior to emulsification and emulsion color.
  • colorless functionalized waxes do not produce colorless emulsions.
  • the waxes most envisioned to be used in industry are those functionalized waxes which are most easily emulsified into fine-sized particles with narrow size distribution.
  • maleated polypropylene and oxidized polyethylene are the preferred waxes for use with the present invention.
  • this process is especially advantageous due to its broad applicability.
  • the specific functionality and process of functionalizing the wax does not limit the use of this novel process, as long as the functionalized wax is emulsifiable.
  • functionalized polyethylene must have an acid number greater than 10 and functionalized polypropylene must have an acid number greater than 30 to be emulsifiable.
  • a preferred emulsion of functionalized polyolefin wax to be treated with this process will have an average particle diameter of less than 0.1 micron and a polydispersity value less than 0.5 when measured by dynamic light scattering.
  • Polydispersity is defined by dividing the second cumulant of the intensity autocorrelation function by the square of the first cumulant.
  • the more preferred emulsified maleated polypropylene wax has an average particle diameter of 0.04 to 0.08 micron, while the more preferred emulsified oxidized polyethylene wax typically has an average particle diameter of 0.02 to 0.06 micron.
  • Wax emulsions are referred to as nonionic, anionic or cationic, depending on the nature of the surfactant used to prepare the emulsion.
  • the surfactants most preferred include ethoxylated nonylphenol and ethoxylated linear or secondary alcohols.
  • a strong base such as sodium or potassium hydroxide is typically used in the formulation to neutralize the wax acid functionality and enhance the hydrophilic nature of the wax.
  • the resulting emulsion will have a pH above 8, often between a pH of 9 and 1 1 .
  • Anionic emulsions are generally very highly colored. For these reasons, it is generally preferred for this process to be carried out using a nonionic wax emulsion. This process is also preferably carried out in the substantial absence of amines in both anionic and nonionic systems, since amines render the process substantially less efficient.
  • Other materials may also be present in the functionalized wax emulsion as long as they do not significantly interfere with the decolorizing process.
  • strong reducing agents such as sodium metabisulfite, commonly used in wax emulsions to improve translucency through decreased particle size and to somewhat lower the color, does not interfere with the applicability of the present invention.
  • typical materials which may be present in emulsions used with this process include biocides, fungicides and antifoam agents.
  • Peroxygen-type bleaches those which can form hydrogen peroxide when dissolved in water, and chlorine-type bleaches were the oxidizing agents found most effective to reduce emulsion color.
  • oxidizing agents used in treating wax emulsions in the present invention are the water soluble peroxides, hypochlorites, perborates, persulfates, ozone and peracetic acid.
  • the monohydrate perborates are preferred over tetrahydrate perborates.
  • Water soluble refers to materials which dissolve in water, with or without the presence of a small excess of undissolved particulates. Ozone is generally bubbled through the emulsion.
  • oxidizing agents include hydrogen peroxide and alkali metal salts of peroxide, hypochlorite, perborate and persulfate, with the sodium and potassium salts being the preferred alkali metal salts.
  • oxidizing agents include hydrogen peroxide and sodium hypochlorite.
  • hydrogen peroxide is the most preferred oxidizing agent since hydrogen peroxide reduces emulsion color more effectively than sodium hypochlorite, is especially safe to work with in aqueous solution, is easily available, and has such environmentally friendly decomposition products.
  • oxidizing agents used in this process reported in weight percent, based on the total emulsion weight: between 0.1 percent and 20 weight percent hydrogen peroxide, preferably between 0.3 percent and 3 weight percent, most preferably between 1 percent and 2 weight percent; between 0.1 percent and 10 weight percent peroxide salt, preferably between 0.1 percent and 5 weight percent; between 0.1 percent and 30 weight percent hypochlorite salt; between 0.1 percent and 10 weight percent perborate salt, preferably between 0.1 percent and 5 weight percent; between 0.1 percent and 10 weight percent persulfate salt, preferably between 0.1 percent and 5 weight percent; between 2.4 X 10 * moles/hour and 9.6 X 10 2 moles/hour ozone continuously bubbled into each lOOmL of emulsion (continuous bubbling is necessary since ozone is not stable in alkaline solution); between 0.1 percent and 20 weight percent peracetic acid, preferably between 0.3 percent and 3 weight percent, most preferably between 1 percent and 2 weight percent.
  • the practice of this invention using hydrogen peroxide as the oxidizing agent as an illustrative example, consists of adding an aqueous solution of 30 percent hydrogen peroxide to the previously prepared emulsion of functionalized polyolefin wax in a suitable stirred vessel which is either open or closed to the atmosphere, and with the emulsion at the temperature of optimum color reduction. The wax emulsion/hydrogen peroxide mixture is then left stirring for a suitable time to reduce the emulsion color.
  • the exact method of introduction of the hydrogen peroxide solution to the emulsion is not critical, but stirring upon introduction is recommended to keep from shocking the system. In fact, this process can be practiced by the addition of the oxidizing agent or bleach during the emulsification cool-down cycle. It is important, however, that the introduction of the oxidizing agent occur after the formation of the wax emulsion. Also, the oxidizing agent should not be present during formation of the wax emulsion.
  • the optimum time required to effect significant color reduction depends upon the nature of the oxidizing agent, the agent concentration in the wax emulsion, and the emulsion temperature.
  • the bleaching effect begins immediately upon introduction of the oxidizing agent into the emulsion.
  • the reaction time is preferably between 5 minutes and seven days. At least 5 minutes of mixing is generally needed for the oxidizing agent to have contact with a significant amount of wax and it is generally impractical to run a reaction for more than 7 days.
  • the reaction time is more preferably between 5 and 90 minutes, most preferably between 10 and 40 minutes.
  • a minor amount of oxidizing agent can remain in the emulsion for extended periods and slightly reduce the color over time. It should be noted, however, that a significant amount of oxidizing agent should not remain in the emulsion when it will be stored for any significant length of time due to the dangerous accumulation of oxygen.
  • the temperature range for this process is between above the freezing point and below the boiling point of the emulsion and below the softening point of the wax. Besides the fact that oxidizing agents cannot be adequately mixed into a frozen emulsion, it may negatively affect the emulsion application performance to actually freeze the emulsion during the color reduction process. Likewise, temperatures above the boiling point of water or above the softening point of the wax can be detrimental to the emulsion due to changing the emulsion balance upon evaporation of water and/or negative affects to the application performance of the emulsion upon softening of the wax. The optimum conditions of temperature, concentration, and time will depend on the specific oxidizing agent used.
  • the emulsion is heated to a temperature of between 50°C and 90°C, most preferably between 60°C and 80°C. This heat is preferably residual heat that was added to the emulsion system during the formation of the emulsion and the decolorization takes place during cool down.
  • Controlled pressure is not required for the practice of this invention as long as the temperature is kept within an acceptable range.
  • This invention can be practiced at ambient atmospheric pressure with an open vessel or at controlled pressure in a closed vessel. If a closed vessel is used, it should be suitably pressure rated when peroxygen-type bleaching agents are used due to the fact that decomposition of the bleaching agent occurs with release of oxygen gas.
  • the process for reducing the color of emulsions of functionalized polyolefin waxes can be practiced as part of an overall process for producing a low colored emulsion of functionalized polyolefin wax.
  • This overall process would comprise the steps of firstly functionalizing a polyolefin wax, secondly emulsifying the functionalized polyolefin and thirdly reducing the color of the emulsion of functionalized polyolefin wax according to the present process.
  • Functionalization of polyolefins can be accomplished by the addition of carboxylic acid groups to or the oxidation of a polyolefin. Oxidation is accomplished by various air oxidation methods which employ steps for hydrogenating and oxidizing low molecular weight polyolefin fragments.
  • the addition of dicarboxylic anhydride/acid groups to polyolefins is accomplished by reacting low molecular weight polyolefins with ethylenically unsaturated polycarboxylic acid, anhydrides or esters thereof, in the presence of a free radical source.
  • the functionalization methods are disclosed in U.S. Patents 3,329,667; 3,519,588; 2,879,239; 3,480,580 and 3,642,722.
  • the emulsification step is accomplished by various techniques including adding molten functionalized wax to hot aqueous surfactant solution, adding hot aqueous surfactant solution to molten functionalized wax, or using pressure equipment if the wax melt point is greater than the boiling point of water.
  • the emulsion mixture is typically stirred for 30 minutes prior to the cool-down phase.
  • the herein disclosed method for reducing the color of an emulsion of functionalized polyolefin wax can be conducted during the cool-down phase of the emulsification process or it can be conducted subsequent to cool-down.
  • the emulsion of functionalized polyolefin wax produced according to the present invention will preferably have an essentially colorless translucent appearance having a C* value of at least 8.5, an average particle diameter less than 0.1 micron and a polydispersity of less than 0.5.
  • the molecular weight (weight average) of the functionalized polyolefin wax suspended in the emulsion will typically be greater than 1 ,000, preferably greater than 2,000.
  • the low colored emulsion produced according to the present invention can be added to floor polish formulations to yield a floor polish product having the aesthetically pleasing essentially white color desired for marketability of floor polish which also dries to a durable, buffable, scuff resistant and slip resistant film of floor polish when applied to a floor.
  • the following examples are intended to illustrate the present invention but should not be interpreted as a limitation upon the reasonable scope thereof.
  • EPOLENE E-43 is a maleated polypropylene wax from Eastman Chemical Company with typical properties including a Gardner Color of 1 1 , acid number of 47, Mw of 9100, ring and ball softening point of 157°C and specific gravity of 0.934.
  • EPOLENE E-10 is an oxidized polyethylene wax from Eastman Chemical Company with typical properties including a Gardner Color of 2, acid number of 15, Mw of 6100, ring and ball softening point of 106°C and specific gravity of 0.942.
  • EPOLENE E-14 is an oxidized polyethylene wax from Eastman
  • EPOLENE E-15 is an oxidized polyethylene wax from Eastman Chemical Company with typical properties including a Gardner Color of 2, acid number of 16, Mw of 4200, ring and ball softening point of 100°C and specific gravity of 0.925.
  • EPOLENE E-20 is an oxidized polyethylene wax from Eastman Chemical Company with typical properties including a Gardner Color of 2, acid number of 17, Mw of 7500, ring and ball softening point of 1 1 1 °C and specific gravity of 0.960.
  • AC-540 is an ethylene/acrylic copolymer wax from Allied Signal, Inc., with typical properties including an acid number of 40, Mettler drop point (ASTM D3954) of 108°C, and specific gravity of 0.93.
  • AC-392 is a high density oxidized ethylene homopolymer wax from Allied Signal, Inc.
  • Allied Signal, Inc. with typical properties including an acid number of 30, Mettler drop point of 138°C, and specific gravity of 0.99.
  • IGEPAL CO-710 and CO-630 are ethoxylated nonylphenol surfactants from Rhone-Poulenc which have hydrophilic-lipophilic balance (HLB) values of 13.6 and 13.0, respectively.
  • HLB hydrophilic-lipophilic balance
  • Unreacted hydrogen peroxide was determined using cerium sulfate titration with a Ferrion indicator obtained from Aldrich.
  • Colorimetric values for each wax emulsion sample were determined using a reflectance method developed by the applicants. Approximately 70mL of emulsion was poured into a sample cell having an optically flat bottom useful for spectral measurements. The petri dish-shaped sample cell was ca. 8.5 cm in diameter and 2cm deep. The optically flat bottom plate was approximately 4mm thick. The same sample cell was used for all colorimetric evaluations, and was washed with deionized water and blown dry with nitrogen between sample evaluations.
  • the reflectance spectra were measured using a Minolta CM-2002 Reflectance Spectrometer. Simultaneous and essentially instantaneous illumination and detection throughout the visible spectral region (400 to 700 nm) was achieved with a pulsed xenon arc lamp and a silicon photodiode array with a spectral filter array. Specular reflection was excluded by means of an internal light trap. Five arbitrary measurements were made of each sample aliquot over different regions of the sample container, and the averages of these five measurements were reported.
  • CIE Commission Internationale De L'Eclairage
  • Particle size was determined by quasi-elastic light scattering experiments.
  • the neat emulsions were diluted in deionized water prior to measurement.
  • Individual ingredient levels in emulsion recipes are reported as parts by weight. Weight percent can be determined for each ingredient by dividing the parts by weight by the sum of all the ingredients' parts by weight, and multiplying by 100 percent.
  • EXAMPLE 1 This example illustrates that significant color reduction is effected by the addition of aqueous solutions of hydrogen peroxide to emulsions of maleated polypropylene at room temperature and pressure.
  • a series of samples were prepared by stirring the appropriate amount of aqueous hydrogen peroxide solution (30 percent H 2 0 2 ) into aliquots of the emulsion previously placed in 8 oz. sample jars.
  • Controls at each hydrogen peroxide level were also prepared by diluting separate emulsion aliquots with comparable amounts of deionized water.
  • the CIE chromaticity value, C*, using the D65 illuminant and 10 degree observer for each emulsion was evaluated the day the samples were prepared, and after seven days. Significant bubbling occurred in samples containing 5 and 10 grams of added hydrogen peroxide solution, and the seven day time frame was chosen since bubbling had sufficiently diminished by that time so that colorimetry could be performed without significant interference from bubbles in the emulsion. Examination of the emulsions by eye showed that significant color reduction had occurred relative to the controls, and the extent of color reduction followed the amount of hydrogen peroxide added. These results are shown in Table I. Table I.
  • This example illustrates that significant color reduction of an emulsion of maleated polypropylene is effected by adding aqueous hydrogen peroxide at room temperature in the absence of ultraviolet light.
  • Four samples taken from the batch of typical nonionic emulsion of E-43 used in Example 1 were prepared by placing 6 g of the E-43 emulsion in each of four 4 dram vials. Two of the four vials were wrapped with aluminum foil to exclude light. One of the aluminum foil wrapped vials and one of the unwrapped vials served as controls, and 0.5 g of deionized water were added to each. To the other two vials, 0.5 g of 30 percent aqueous hydrogen peroxide were added.
  • This example illustrates that color reduction using hydrogen peroxide occurs with the formation of oxygen gas, and that formation of this gas is not due to reaction with the surfactant in the wax emulsion.
  • a 50 ml aliquot of the batch of nonionic emulsion of E-43 used in Example 1 was placed in a 100 ml flask. The sample was purged with nitrogen and sealed with a rubber septum. The contents were stirred via a magnetic stir bar at room temperature. A syringe was used to transfer 3 ml of 30 percent aqueous hydrogen peroxide to the emulsion sample in the flask. The emulsion sample was stirred continuously for two hours at which point the headspace over the emulsion was analyzed for gas composition.
  • Emulsions of Epolene E-10, Epolene E-14, Epolene E-1 5, and Epolene E-20 were prepared using the "direct pressure" technique according to the typical formulation recipe of 40 parts wax, 12 parts Igepal CO-710, 1 part KOH (87 percent), and 0.4 parts of sodium metabisulfite.
  • Control samples were prepared by diluting 50 g of each emulsion with 5 g of deionized water in 8 oz sample jars.
  • Hydrogen peroxide treated samples were prepared by adding 5 g of 30 percent aqueous hydrogen peroxide to
  • EXAMPLE 5 This example demonstrates that hydrogen peroxide is useful in reducing color of high density oxidized polyethylene wax emulsions.
  • An emulsion of Allied Signal, Inc., AC-392 was prepared using the "direct pressure" technique according to the typical formulation recipe consisting of 40 parts wax, 12 parts Igepal CO-710, 1 .5 parts KOH (87 percent), 0.4 parts of sodium metabisulfite, and 99 parts of deionized water.
  • a control sample was prepared by diluting 50 g of the AC-392 wax emulsion with 5 g of deionized water in an 8 oz. sample jar.
  • a hydrogen peroxide treated sample was prepared by adding 5 g of 30 percent aqueous hydrogen peroxide to 50 g of AC-392 emulsion in an 8 oz. sample jar. Both control and sample preparations were made and maintained at room temperature.
  • aqueous hydrogen peroxide is effective in reducing the color of emulsions of maleated polypropylene waxes, even in the presence of a strong reducing agent, sodium metabisulfite.
  • An emulsion was prepared by adding 0.4 parts sodium metabisulfite to the batch of E-43 used in Example 1 .
  • a series of samples were prepared from this emulsion by stirring appropriate amounts of aqueous hydrogen peroxide solution (30 percent H 2 0 2 ) into aliquots of the emulsion in 8 oz. sample jars. Controls at each hydrogen peroxide level were also prepared by diluting separate emulsion aliquots with comparable amounts of deionized water. The chromaticity value for each emulsion was evaluated the day the samples were prepared, and after seven days. The data are presented in Table II.
  • EXAMPLE 7 This example illustrates that sodium hypochlorite is useful to reduce color of maleated polypropylene emulsions, but not as useful as hydrogen peroxide. 20 g of 10 percent sodium hypochlorite solution was stirred into
  • EXAMPLE 8 This example illustrates that ozone is effective at reducing the color of maleated polypropylene emulsions.
  • a typical nonionic emulsion of maleated polypropylene, consisting of 40 parts Epolene E-43, 12 parts Igepal CO-630, 3.6 parts potassium hydroxide (87 percent), and 130 parts of deionized water was prepared. 100 ml of E-43 emulsion was placed in a 200 ml flask fitted with a gas dispersion stone and connected to an ozone generator. Air containing approximately 2.3 g/hr ozone was bubbled through the emulsion at room temperature for one hour. The resulting emulsion had lost it's initial brown color and was a transparent water white color after treatment.
  • This example illustrates that this invention is useful in reducing the color of functionalized amorphous polyolefins.
  • a typical nonionic emulsion was prepared of a maleated amorphous propylene/ethylene copolymer, consisting of 40 parts wax, 12 parts Igepal CO-630, 5 parts potassium hydroxide (87 percent), and 133 parts of deionized water, using the "direct pressure" technique.
  • the amorphous copolymer, EASTOFLEX PI 023 is commercially available from Eastman
  • P1023 was maleated in a batch process at 195°C under a nitrogen blanket with constant stirring.
  • the polymer was brought up to temperature, and a mixture of 14 parts maleic anhydride, 3.2 parts di-t-butyl peroxide, and 1 part by weight tetralin (chain transfer agent) was slowly dripped into the molten polymer from a dropping funnel. After workup, the polymer had an acid number of 58 mg KOH/g polymer and a melt viscosity of 450 cp at 190°C.
  • the emulsion prepared from this maleated amorphous polymer was brown and translucent in appearance, and a 100 ml aliquot of the emulsion was treated with ozone according to the procedure described in Example 8 to yield a white translucent emulsion.
  • This example illustrates that this process can be practiced by addition of the oxidizing agent during the emulsification cool-down cycle.
  • Example 1 190 g of the E-43 emulsion used in Example 1 was charged to a 300 ml stirred stainless steel pressure reactor. The reactor was sealed and heated to 90°C with constant stirring in order to achieve typical emulsification conditions. Once at temperature, the heating mantle was removed, the reactor unsealed, and 10 g of 30 percent aqueous hydrogen peroxide was poured into the emulsion. The reactor was then sealed again and left to cool with stirring. As in a typical emulsification cool-down cycle, it took ca. 2 hours to cool from 90°C down to 40°C, accomplished without running cooling water to expedite the cooling process. A pressure buildup of 70 psi occurred, and this was vented prior to opening the reactor. Upon opening the reactor, quite a bit of foam was evident, and the resulting emulsion color was significantly reduced. EXAMPLE 1 1
  • Epolene E-43 nonionic emulsion was prepared according a typical formulation consisting of 40 parts Epolene E-43 wax, 12 parts Igepal CO-630, a little less than 3.6 parts potassium hydroxide (87 percent), and 84 parts of deionized water was prepared by the "direct pressure" technique. 400 grams of E-43 emulsion was removed from the bulk batch and titrated with 2N KOH solution until the emulsion pH was 9.5. This titrated emulsion was then split, with 198 g being charged to the pressure reactor and 198 g placed in a sample jar along with 2 g of deionized water. This water-diluted sample served as the reference for the color measurement of the peroxide-treated sample. The water-diluted standard had a C* value (D65 illuminant, 10° observer) of 6.18.
  • the pressure reactor was sealed and heated with stirring to the run temperature of 50°C. Once at temperature, the pressure vessel was unsealed, opened and 2 g of 30 percent aqueous hydrogen peroxide solution was poured in, resulting in a weight concentration of hydrogen peroxide in the emulsion of 0.3 weight percent. The pressure vessel was immediately reseated, and temperature was maintained for 30 minutes. Stirring was maintained at a fixed rate except when the peroxide was actually added. The pressure increase was monitored via an attached pressure gauge, and the maximum pressure buildup of 5 psi occurred ca. 15 minutes after adding the hydrogen peroxide.
  • the heating mantle was removed and water run through the cooling coils in the reactor until the temperature was below 40°C. The excess pressure was then carefully bled off, the reactor opened, and the contents poured into a sample jar.
  • the dispersion pH after reaction, and residual peroxide were evaluated immediately after preparation.
  • the emulsion pH decreased from 9.5 to 8.8 upon treatment with hydrogen peroxide, and ca. 30 percent of the originally added hydrogen peroxide remained in solution after reaction.
  • the hydrogen peroxide-treated sample had a C* value of 8.00.
  • the effective particle diameter of the emulsion particles was measured to be 53.8 nm.
  • This example illustrates that at high pH, high reaction temperature, and with a long reaction time significant color reduction occurs when a maleated polypropylene emulsion is treated with high levels of hydrogen peroxide solution.
  • Example 1 1 A 400 g aliquot of the batch emulsion from Example 1 1 was titrated to pH 1 1 with 2N KOH. This titrated emulsion was then split, with 180 g being charged to the pressure reactor and 180 g placed in a sample jar along with 20 g of deionized water. This water-diluted sample served as the reference for the color measurement of the peroxide-treated sample. The water-diluted standard had a C* value (D65 illuminant, 10° observer) of 6.22. After charging with the emulsion, the pressure reactor was sealed and heated with stirring to the run temperature of 90°C.
  • the pressure vessel was unsealed, opened and 20 g of 30 percent aqueous hydrogen peroxide solution was poured in, resulting in a weight concentration of hydrogen peroxide in the emulsion of 3 weight percent.
  • the pressure vessel was immediately resealed, and temperature was maintained for 90 minutes. Stirring was maintained at a fixed rate except when the peroxide was actually added.
  • the pressure increase was monitored via an attached pressure gauge, and the maximum pressure buildup of 220 psi occurred ca. 15 minutes after adding the hydrogen peroxide.
  • the heating mantle was removed and water run through the cooling coils in the reactor until the temperature was below 40°C. The excess pressure was then carefully bled off, the reactor opened, and the contents poured into a sample jar.
  • the dispersion pH after reaction, and residual peroxide were evaluated immediately after preparation.
  • the emulsion pH decreased from
  • the hydrogen peroxide-treated sample had a C* value of 10.84.
  • the effective diameter of the resultant emulsion particles was measured to be 63.8 nm.
  • This example illustrates that at a medium pH, medium reaction temperature, and with an hour reaction time, significant color reduction occurs when a maleated polypropylene emulsion is treated with high levels of hydrogen peroxide solution.
  • Example 1 1 A 400 g aliquot of the batch emulsion from Example 1 1 was titrated to pH 10.3 with 2N KOH. This titrated emulsion was then split, with 189 g being charged to the pressure reactor and 180 g placed in a sample jar along with 1 1 g of deionized water. This water-diluted sample served as the reference for the color measurement of the peroxide-treated sample. The water-diluted standard had a C* value (D65 illuminant, 10° observer) of 6.70.
  • the dispersion pH after reaction, and residual peroxide were evaluated immediately after preparation.
  • the emulsion pH decreased from 10.3 to 8.9 upon treatment with hydrogen peroxide, and ca. 5.15 percent of the originally added hydrogen peroxide remained in solution after reaction.
  • the hydrogen peroxide-treated sample had a C* value of 10.79.
  • the effective diameter of the resultant emulsion particles was measured to be 54.4 nm.
  • Example 1 1 A 400 g aliquot of the batch emulsion from Example 1 1 was titrated to pH 9.5 with 2N KOH. This titrated emulsion was then split, with 180 g being charged to the pressure reactor and 180 g placed in a sample jar along with 20 g of deionized water. This water-diluted sample served as the reference for the color measurement of the peroxide-treated sample. The water-diluted standard had a C* value (D65 illuminant, 10° observer) of 6.70.
  • the pressure reactor was sealed and heated with stirring to the run temperature of 90°C. Once at temperature, the pressure vessel was unsealed, opened and 20 g of 30 percent aqueous hydrogen peroxide solution was poured in, resulting in a weight concentration of hydrogen peroxide in the emulsion of 3 weight percent. The pressure vessel was immediately resealed, and temperature was maintained for 90 minutes. Stirring was maintained at a fixed rate except when the peroxide was actually added. The pressure increase was monitored via an attached pressure gauge, and the maximum pressure buildup of 165 psi occurred ca. 15 minutes after adding the hydrogen peroxide.
  • the heating mantle was removed and water run through the cooling coils in the reactor until the temperature was below 40°C.
  • the excess pressure was then carefully bled off, the reactor opened, and the contents poured into a sample jar.
  • the contents of the reactor was highly viscous, comparable in flow behavior to petroleum jelly.
  • This example illustrates the importance of decolorizing the wax only after it has been emulsified by showing that addition of oxidizing bleaching agents during preparation of functionalized polyolefin wax emulsions actually increases the emulsion color rather than decreasing color.
  • the first emulsion recipe which served as a control, consisted of 40 parts wax, 12 parts Igepal CO-630, 3.6 parts potassium hydroxide (87 percent), and 83.4 parts of deionized water.
  • the pressure vessel was charged with the ingredients, sealed, heated to 175°C with constant stirring and left at temperature for 30 minutes. The heating mantle was then removed and cooling water was circulated through coils in the reactor until the product temperature was 40°C.
  • the reactor was then opened and the control emulsion was poured into a glass sample jar. This emulsion had pH after preparation of 9.06, and a CIE C* value (D65 illuminant, 10 degree observer) of 5.02.
  • the second emulsion was prepared according to the recipe of 40 parts of Epolene E-43 wax, 12 parts Igepal CO-630, 3.6 parts potassium hydroxide (87 percent), 1 .2 parts of sodium perborate monohydrate, and 85.2 parts deionized water.
  • a mole of perborate yields a mole of sodium metaborate and a mole of hydrogen peroxide in aqueous solution, so on a mass basis the monohydrate material added to the emulsion is approximately 32 percent hydrogen peroxide. Therefore, in this formulation 1 .2 parts by weight of sodium perborate monohydrate is equal to approximately 0.3 weight percent in the emulsion.
  • the sample emulsion pH was 9.89, and the CIE C* value (D65 illuminant, 10 degree observer) was 3.36.
  • EXAMPLE 17 This example illustrates that peracetic acid is an effective oxidative bleaching agent useful in the present process to reduce the color of aqueous emulsions of functionalized polyolefins.
  • EXAMPLE 18 This example illustrates the strong positive correlation between the amount of color of functionalized wax and emulsion color. More specifically, this example shows that a lower Gardner Color value, the colorimetric value used to measure the amount of color in solid waxes, results in a higher value of C* for a typical emulsion, where the higher value of C* indicates a lower emulsion color.
  • Typical non-ionic emulsions were prepared from each of four lots of Epolene E-43 wax using the "direct pressure" technique consisting of 40 parts by weight of wax, 12 parts of CO-630 surfactant, 27.4 parts of 2.045N KOH solution, 0.4 parts of sodium metabisulfite, and 52.8 parts of deionized water.
  • the wax was taken from four different lots of Epolene E-43 wax having different Gardner color values. Repeat emulsions were prepared for each wax lot to ensure that the observed differences in emulsion C* were not due to variability in preparing the emulsions. A linear least-squares regression fit to a plot of
  • An emulsion of the extracted pellets was prepared according to the "direct pressure" technique consisting of 40 parts by weight of wax pellets, 12 parts Igepal CO-630 surfactant, 2.1 parts of KOH pellets (87 percent), and 81 .1 parts deionized water. After preparation, the emulsion was milky and highly colored. The C* value of the emulsion was measured to be 3.51 .

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé pour diminuer la couleur d'une émulsion de cire polyoléfinique modifiée chimiquement en traitant l'émulsion par un agent oxydant hydrosoluble à une température supérieure au point de congélation et inférieure au point d'ébullition et au point de ramolissement de la cire. On obtient ainsi une émulsion sensiblement incolore qui est utile comme additif pour des cires pour le plancher et pour d'autres produits de revêtement.
PCT/US1996/015013 1995-09-21 1996-09-19 Procede pour diminuer la couleur d'une emulsion contenant une cire polyolefinique modifiee chimiquement WO1997011110A1 (fr)

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WO2002090403A1 (fr) 2001-05-06 2002-11-14 Honeywell International, Inc. Polypropylene a base de maleate presentant des proprietes ameliorees
US20120171466A1 (en) * 2009-08-26 2012-07-05 Sika Technology Ag Hot-melt adhesives with improved adhesion on low-energy surfaces

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WO2002060965A2 (fr) * 2000-12-12 2002-08-08 Baker Hughes Incorporated Polymeres, copolymeres et derives de polypropylene isotactiques de faible poids moleculaire et substances preparees au moyen de ceux-ci
US20050260244A9 (en) * 2003-11-12 2005-11-24 Sumitomo Chemical Company, Limited Pesticidal particle
US20050267234A1 (en) * 2004-05-19 2005-12-01 International Paper Company Resistant printing ink system
US20060069188A1 (en) * 2004-09-29 2006-03-30 Klosiewicz Daniel W Processes for producing functionalized polyolefin emulsions
US20060069209A1 (en) * 2004-09-29 2006-03-30 Klosiewicz Daniel W Heat stable functionalized polyolefin emulsions
JP7037108B2 (ja) * 2017-12-15 2022-03-16 東洋紡株式会社 金属板貼合せ成形加工用着色二軸延伸ポリエステルフィルム
CN113929800A (zh) * 2021-09-27 2022-01-14 天津大学仁爱学院 一种氧化聚乙烯蜡的生产方法及装置

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WO2002090403A1 (fr) 2001-05-06 2002-11-14 Honeywell International, Inc. Polypropylene a base de maleate presentant des proprietes ameliorees
US20120171466A1 (en) * 2009-08-26 2012-07-05 Sika Technology Ag Hot-melt adhesives with improved adhesion on low-energy surfaces
US9359534B2 (en) * 2009-08-26 2016-06-07 Sika Technology Ag Hot-melt adhesives with improved adhesion on low-energy surfaces

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AU7075896A (en) 1997-04-09

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